Complex chromium compounds of azo dyestuffs



Patented Mar. 17, 1925.

ENT OFFICE.

HERMANN FRITZSCHE, EMIL, REBER, AND IFRITZ STRAUB, OF BASELQSW'ITZERLAND,

ASSIGNORS '20 .THE SOCIETY SWITZERLAND.

iF CHEMICAL INDUSTRY IN "BASLE, OF "BASEL,

l 'ooMPLEx CHROMIUM COMPOUNDS or AZO nvns'rurrsi;

No Drawing.

To all whom it may concern:

Be it known that We, HERMANN FRITZSCHE, EMIL Renee, and Furrz STRAUB, all citizens of the Swiss Republic, andresiding it Basel,

5 Switzerland, have invented new and useful Complex Chromium Compounds of Azo Dyestuffs, of which the following is a full, clear, and exact specification.

The present invention relates to new complex chromium compounds of azo dyestufl's which form valuable acid coloring matters for the production of fast tints on the animal fiber. It comprises the dyed fabrics or other materials, dyed With the new-dyestuffs,

as well as the dyestnlfs themselves.

It has been found that new complex comgpunds of azo d 'estufi's with chromium may obtained by t 10 action of chroming agents on the O-hydroXyaZO-dyestufls, which are obtained by coupling 1-aryl-5-pyrazolones ide on wherein carrying an SO NH group in their aryl nucleus with O-hydroxydiazo compounds. Such a chroming, agent is, f r instance, the chromie oxide (1&0, or respectively its hydroxor the combination of these bodies with alkalics or Weak acids.

The new products are therefore the complex chromium compounds of azo dyestuffs of the eneral formula: RN.-:NR signifies a 1-aryl-5-pyrazolone carrying an SO NH group in its aryl nucleus, and R an aryl nucleus containing an OH group in orthoposition to the azo bridge. They form dark powders having more or less a bronze reflection, soluble in water on addition of alkali to orange-red to blue-red solutions, dyeing WOOl in an acid bath orange to blue-red tints of excellent fastness to fullin and to light and of high purity. The foll owing examples illustrate the invention Without, however, limiting the same.

Ewrzmple 1-.

510 parts of the dyestuif obtained by coupling diazotized 2-amino-Lhydroxyhenzene- 4-chloro-5-sulfonie acid with l-(3-sulfam- I Application filed October 8,

192a. "seriai No. $7,319 1 ido)-phenyl-3-methyl-5-pryazolone are dis-' solved in 6000 parts ofjboiling water; a quantity of chromium fluoride correspond ing with243 parts of ehr'omiumoxide (Ct dissolved in about 5000 parts of water is then added and the mixtureis heated in a reflux apparatus until the dyestufi' is transformed into its chromium derivativeh 'lhe liquid is evaporated in part'and thedycstufi is precipitated by adding common salt; The

new dyestufl is a brown powder which dis, solves in alkaline water to an oranger'ed solution and dyes wool very uniform orangered tints, fast to washing and light.

Example? l 525 parts of the dyestulf obtained by-coupling the diazo compoundof 1-amino-2-hy droxynapthalenet-sulfonic acid with 1-,(3'- sulfami'do) -phenyl-3-methyl5-pyra z 01 on e are dissolved in 10,000 parts (if-boiling water and there is added a quantity'off chromium formate corresponding with .228 parts of chromium oxide (Ci- 0,); the mixtureds heated in a reflux apparatus untilfthegdyestufi has been transformed into'its chromium derivative. The liquid is eooledniid ,the

chromed dyestufl', which has separatedin the form of a crystalline powder having a bronze reflection, is filtered. It dissolves in alkaline Water to a red solution and'dyes wool in an acid bath'beautiful, verypm'e rose tints which are very fast and of excellent uniformity. i

By substituting for the chromium formats another chroming agent, such as the-acetate the fluoride or chromium oxide, products. 0

like properties are obtained. I

Example 3. H

570 parts of the dyestufi' obtained b coupling the nitrated dlazo compound o Lamino-Q-hydroxyna hthaleneA-sulfonic a c id with l-(3'-sul amide -phenyl-3-methyl-5- pyrazolone are dissolve in about 7000 parts of boiling water and there is added mum tity of chromium fluoride corresponding with 228 .parts of chromium oxide (C230,) the whole is heated in a reflux apparatus until the dyestufl has been transformed into its chromium derivative. On cooling the dyestufi separates in the form of a crystalline powder having a bronze reflection. It

i dissolves in alkaline water to a red solution Ewample 4.

A mixture of 60 parts of chromium oxide (Cr,O,), in the form of freshly precipitated hydrate, 260 parts of caustic potash,

100 parts of glycerine and 420 parts, of

' nearly all the dyestufl has been transfor' complex chromium compounds jazo dyestuffs of the general formula water is heated until the constituents have wholly dissolved; there are then added 2000 parts of water, 525 parts of the dyestufl obtained by coupling the diazo compound of ,l-. amino 2 hydroxynaphthalenelsulfonic 5-pyrazolone and the whole is heated until into the chromium derivative. The mixtur; is then diluted with 6000 parts of cold we." ter, the excess of alkali is neutralized with acetic acid and the dyestuif is precipitated by adding common salt; it is filtered and dried.

What we claim is:

1. As new products the herein described of the -BN=N-R' wherein R si ifies a 1-aryl- 5-pyrazolone carryin an SjNH roup in its aryl nucleus, and an aryl nuc eus containing an OH oup in ortho-position .to the azo brid e, w ich dyestufi's constitute dark owders aving more or less a bronze reflec ion, dissolving in water on addition of alkali to orange-red to blue-red solutions, producing on wool dyed in an acid bath oran eto blue-red tints of high purity and excel ent fastness to fulling and to light.

2. As new products the herein described complex chromium compounds of the azo dyestuffs of the general formula R-N=N-R wherein R si ifies a l-aryl- 5-pyrazolone carrying an S ,N'H, group in its aryl nucelus, and R a mono-sulfonated aryl nucelus containing an OH- group in ortho-position to the azo bridge, which dyestufl's constitute dark powders having more or less a bronze reflection, dissolving in water on addition of alkali to orange-red to blue-red solutions, producin on wool dyed in an acid bath oran e.- to blue-red tints of high purity and exce lent fastness to fulling and to light.

3. As new products the herein described complex chromium compounds of the azo dyestuffs of the, general formula 3-methyl-5-pyrazolone early-11f an SO N group in its aryl nucleus' an R a monosulfonatcd aryl nucleus containing an 'OH group in orthorposition to the i120 bridge, which dyestufls constitute d k owdcrs having more or less a bronze rriiection, dis- RN=N B wherein R signifies a lergsolving in water on addition of alkali to orange-red to blue-red solutions, producing on wool dyed in an acid bath orange to blue-red tints of high purity and excellent fastness to fulling and to light.

4. As new products the herein described complex. chromium compounds of the azo dyestuffs of the general formula R N -N-R wherein R signifies a 1-aryl- 3-methyl-5-pyrazolone carrying an sO NH group in its aryl nucleus, and R a 2-hyroxynaphthalene-ksuifonic acid nucleus where the azo bridge adheres to the l-posi tion of the naphthalene nucleus, which dyestuds constitute dark powders having more or less a bronze reflection, soluble in water on addition of alkali to red to bluered s0lu tic r producing on wool dyed in an. acid be :1) red to blue-red tints of hi h purity and excellent fastness to fulling an to light.

ii. As new products the herein described cauuplcx chromium compounds of the azo dyestuffs of the general formula R-dl' N-R wherein. R signifies a 1- (lsulfamido) -aryl 1 8 meth vl5 -pyrazolone,

and R a hydr'oxynaphthalencl-sulfonic acid nucleus where the azo bridge adheres to the 1' os'ition of the naphthalene nucleus, which yestufl's constitute dark powders having more or less a bronze reflection, soluble in water on addition of alkalito red to blue-red solutions, producing on wool dyed in an acid bath red to blue-red tints of high purity and excellent fastness to fulling and a to light. I r 6. As new products the hereindescribed complex chromium compounds of the dyestuil of the general formula 10, Materials dyed with this new dyestufi's hey, 1923, in the presence of two subscribin of claim wltnessvsu 1L Materials dyed with the new dye/stuffs HER-MANN FRITZSCHE. of claim 5. EMIL REBER. 5 12. Mahrrials dyed with the new dyestuffs FRITZ STRAUB.

of claim 6. Witnesses:

In witness whereof we have hereunto AMAND BRAUN,

signed our names this 27th day of Septem- JOSEPH SiiTTERuN. 

